CN113956145B - Preparation method of 2, 7-dimethyl-2, 4, 6-octatriene-1, 8-dialdehyde - Google Patents

Preparation method of 2, 7-dimethyl-2, 4, 6-octatriene-1, 8-dialdehyde Download PDF

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CN113956145B
CN113956145B CN202111149953.0A CN202111149953A CN113956145B CN 113956145 B CN113956145 B CN 113956145B CN 202111149953 A CN202111149953 A CN 202111149953A CN 113956145 B CN113956145 B CN 113956145B
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dialdehyde
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CN113956145A (en
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王嘉辉
张涛
沈宏强
刘英瑞
张弈宇
宋军伟
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Wanhua Chemical Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
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Abstract

The invention relates to a preparation method of 2, 7-dimethyl-2, 4, 6-octatriene-1, 8-dialdehyde, which takes acidolysis 3, 6-dioxane/aryloxy-2, 7-dimethyl-4-octenedialdehyde as raw material and adopts solid base as catalyst to synthesize deca-dialdehyde. The preparation method provided by the invention has the following advantages: (1) The selectivity of the process product is more than 99%, the content of the dodecenoic acid impurity in the product is less than 100ppm, the acidic impurity is reduced, and the storage stability is greatly improved; (2) The residual amount of the metal ions of the obtained product is less than 10ppm, the product can reach the standard without post-treatment, and the problem of complex metal ion purification operation in the traditional homogeneous catalysis system is effectively solved; (3) The method is simple to operate, and the alkaline solid catalyst is adopted to replace a common alkali metal aqueous solution system, so that the problem of treatment of alkali-containing wastewater can be effectively solved, the problem of separation and application of the catalyst can be solved, and continuous production of deca-dialdehyde can be realized.

Description

Preparation method of 2, 7-dimethyl-2, 4, 6-octatriene-1, 8-dialdehyde
Technical Field
The invention belongs to the field of fine chemical engineering, and particularly relates to a preparation method of 2, 7-dimethyl-2, 4, 6-octatriene-1, 8-dialdehyde.
Background
2, 7-dimethyl-2, 4, 6-octatriene-1, 8-dialdehyde, which is called as decadialdehyde for short, is an important key intermediate for synthesizing carotenoid, and plays a key role in synthesizing pigments such as beta-carotene, canthaxanthin, astaxanthin and the like. Carotenoids can be used as pharmaceutical, coloring, food additives and feed additives for pharmaceutical, food, cosmetic and aquaculture. Along with the increasing application of carotenoid in China, the synthesis research of 2, 7-dimethyl-2, 4, 6-octatriene-1, 8-dialdehyde is of great significance.
In the reaction of synthesizing deca-dialdehyde in Chinese patent CN100460378C, sodium bicarbonate aqueous solution is used as alkali, the reaction temperature is selected to be 70-90 ℃, sodium bicarbonate is well known to be easily decomposed by heating, the catalytic efficiency of a catalyst in a system is continuously reduced, and the traditional homogeneous catalysis mode is easy to cause metal residues, so that the product quality is reduced.
In European patent EP0784042 (A1), bis (oxalato) borate is used as a catalyst for enol ether condensation reaction, 15% sodium hydroxide solution is added after hydrolysis for elimination reaction, the yield is 67%, and the storage stability of C10 dialdehyde is reduced due to the existence of acidic impurities in the system, so that disproportionation reaction is easy to occur, and the purity of the product is reduced.
In summary, in the method for preparing the deca-dialdehyde by enol ether condensation, the elimination reaction is an important step, and the use of strong base in the known route has higher requirements on equipment and can reduce the product quality of the deca-dialdehyde, and the use of weak base can lead to the increase of three wastes. Therefore, development of a green, environment-friendly, high-quality and low-cost production process is necessary for synthesizing deca-dialdehyde.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a preparation method of 2, 7-dimethyl-2, 4, 6-octatriene-1, 8-dialdehyde, which takes 3, 6-dioxane/aryloxy-2, 7-dimethyl-4-octenedialdehyde (acidolysis for short) as a raw material and adopts solid alkali as a catalyst to synthesize deca-dialdehyde, so that the preparation method has at least the following advantages: (1) The selectivity of the process product is more than 99%, the content of the dodecenoic acid impurity in the product is less than 100ppm, the acidic impurity is reduced, and the storage stability is greatly improved; (2) The residual amount of the metal ions of the obtained product is less than 10ppm, the product can reach the standard without post-treatment, and the problem of complex metal ion purification operation in the traditional homogeneous catalysis system is effectively solved; (3) The method is simple to operate, and the alkaline solid catalyst is adopted to replace a common alkali metal aqueous solution system, so that the problem of treatment of alkali-containing wastewater can be effectively solved, the problem of separation and application of the catalyst can be solved, and continuous production of deca-dialdehyde can be realized.
In order to achieve the above object, the present invention has the following technical scheme:
the invention provides a preparation method of 2, 7-dimethyl-2, 4, 6-octatriene-1, 8-dialdehyde, which adopts raw material acidolysis substances to generate elimination reaction under an alkaline solid catalyst to generate deca-dialdehyde.
In the invention, the acidolysis compound has a structure shown in a formula I, wherein the substituent R can be methyl, ethyl, propyl and phenyl, and preferably methyl.
The alkaline solid catalyst is K 2 O/MgO-ZrO 2 By ZrO 2 As a carrier, mgO as ZrO 2 Tetragonal phase stabilizing substances, K 2 O is a modifier. Wherein, based on the total mass of the alkaline solid catalyst, zrO 2 60-90wt% of MgO, 5-20wt% of K 2 The O content is 5-20wt%.
The preparation method of the catalyst comprises the following steps:
(1) Dropwise adding ammonia water into an aqueous solution of zirconium salt and magnesium salt until a large amount of precipitate is generated, carrying out suction filtration on the precipitate, drying a filter cake, and grinding to obtain solid powder;
(2) And (3) immersing the solid powder obtained in the step (1) in an aqueous solution of soluble potassium salt, and roasting to obtain the required catalyst.
Preferably, the zirconium salt is one or more of zirconium oxychloride, zirconium nitrate or zirconium sulfate.
The mass ratio of the zirconium salt to the ammonia in the ammonia water in the step (1) is 1-10, preferably 2-5; the mass ratio of the zirconium salt to the magnesium salt is 1-10, preferably 3-5; the mass fraction of the aqueous ammonia solution is 10 to 50wt%, preferably 20 to 30wt%.
Preferably, the soluble magnesium salt is magnesium nitrate, magnesium chloride, magnesium sulfate, or the like.
The mass fraction of potassium salt in the aqueous solution of soluble potassium salt in step (2) of the present invention is 1 to 20wt%, preferably 5 to 10wt%; the mass ratio of the potassium salt to the zirconium salt is 0.05-0.5, preferably 0.1-0.3; the impregnation time is 5 to 30 hours, preferably 10 to 20 hours. The roasting temperature is 200-500 ℃, preferably 300-400 ℃; the drying time is 10 to 30 hours, preferably 15 to 20 hours.
The specific surface area of the catalyst in the step (2) of the invention is 100-300m 2 ·g -1 Preferably 120-200m 2 ·g -1 The method comprises the steps of carrying out a first treatment on the surface of the Pore volume is 0.2-1.0 ml.g -1 Preferably 0.5-0.8 ml.g -1 The method comprises the steps of carrying out a first treatment on the surface of the The average pore diameter is 6 to 20nm, preferably 8 to 15nm.
The preparation of the deca-dialdehyde comprises the following steps:
(a) And (3) dissolving the acidolysis material in an organic solvent, pumping the acidolysis material into a fixed bed loaded with the catalyst prepared by the preparation method under certain conditions, and sampling and analyzing the outlet product and impurity content of the reactor.
(b) And (3) desolventizing the obtained reaction liquid, cooling and crystallizing to obtain product crystals, and sampling and measuring the purity of the crystals and the metal residual quantity.
In step (a) of the present invention, the organic solvent is a protic solvent such as methanol, ethanol, isopropanol or hexafluoroisopropanol; aromatic hydrocarbons such as benzene, toluene or xylene; chlorinated hydrocarbons, such as methylene chloride, chloroform, dichloroethane or chlorobenzene; ester solvents such as ethyl acetate, methyl propionate, and mixtures of these solvents. Chlorinated hydrocarbons, particularly preferably dichloromethane, are preferably used as reaction solvent.
The solvent mass of the elimination reaction in step (a) of the present invention is 1 to 50 times, preferably 2 to 20 times, particularly preferably 5 to 10 times the mass of the acidolysis product of the raw material. The mass airspeed of the mixed reaction solution is 10h -1 ～60h -1 Preferably 15h -1 -25h -1 。
The reaction temperature in step (a) of the present invention is-20 to 100 ℃, preferably 0 to 50 ℃, more preferably 10 to 30 ℃, and the reaction pressure is preferably 0.005MPaA to 0.08MPaG, preferably 0.01MPaA to 0.03MPaG.
The bulk density of the catalyst in step (a) is 0.1 g/mL-2.0 g/mL, preferably 0.5 g/mL-1.5 g/mL. The catalyst loading is 5 mL-30 mL, preferably 10 mL-15 mL.
The temperature of the solvent removal in step (b) of the present invention is 20-100deg.C, preferably 30-50deg.C, the pressure is 0.005-1.0 MPaA, preferably 0.01-0.1 MPaA, and the temperature of the reduced crystallization is-20-10deg.C, preferably-10-5deg.C.
Taking R as methyl as an example, the main reaction equation and the side reaction equation described herein are as follows:
main reaction equation (reaction 1):
side reaction equation (reaction 2):
studies have shown that: the acidolysis product is subjected to elimination reaction (reaction 1) and simultaneously the product deca-dialdehyde (marked as an intermediate product) is subjected to disproportionation reaction (reaction 2) under alkaline conditions to generate deca-oleic acid and deca-enol, which are marked as byproducts. The by-product dodecenoic acid is easy to combine with metal ions to generate complex salt, and remains in the deca-dialdehyde product, so that the metal ion content of the product is very easy to be up to the standard.
Studies have shown that: the product of the invention, namely the deca-dialdehyde, is easy to be rich in OH - In the environment of (a), the disproportionation reaction is carried out to generate carboxylate and alcohol, the surface of the catalyst prepared by the invention is an electronic structure of K-O-Mg/Zr, and the active center is O with electricity supply 2- On the one hand, the addition of the atoms and the K element strengthens and stabilizes the load of the active components on the surface of the carrier, and free O is not easy to generate in the elimination reaction of the catalytic acidolysis product 2- Atoms, thereby ionizing to form OH - The environment of (2) can inhibit the occurrence of series side reaction, so that the reaction is not easy to catalyze terminal aldehyde groups to perform disproportionation reaction, the purity of the product is further ensured, and the impurity content in the product is less than 100ppm. The addition of the K element on the other hand causes the surface of the catalyst to form O 2- The eggshell model with all atoms exposed outside improves the unit catalytic efficiency of the active component, has relatively high selectivity under relatively mild reaction conditions, and also ensures that metal ions are wrapped in the core, so that overflow of the metal ions is reduced, the content of the metal ions in the product is controlled, and the product reaches the standard without separation.
Thus, in general, solid base catalysts are employed herein, as are reduced dodecenoic acid content and relatively reduced complex salt content, as well as inhibiting side reactions. Secondly, the catalyst has an eggshell model with the active center outside and the core metal positive ions inside, so that overflow and loss of metal ions are effectively avoided.
The invention has the positive effects that:
1) The solid base catalyst is adopted for elimination reaction to prepare the deca-dialdehyde for the first time, so that the selectivity of the product is more than 99%, the problem of excessive reaction of the product is avoided, and a post-treatment process is not required;
2) The content of the impurity dodecenoic acid in the product after the reaction is less than 100ppm, and the content of the metal ion is less than 10ppm, thereby solving the complex metal ion purification operation in the traditional homogeneous catalysis system. The method comprises the steps of carrying out a first treatment on the surface of the
3) The process is simple to operate, realizes continuous generation of the deca-dialdehyde, and provides a technical basis for high-yield industrialized development.
Detailed Description
The following examples will further illustrate the method provided by the present invention, but the invention is not limited to the examples listed and should include any other known modifications within the scope of the claimed invention.
The reactor used in the examples of the present invention has a height of 100cm and an inner diameter of 5cm, and is provided with a heating temperature control device.
Gas chromatographic analysis conditions: carrying out on-line measurement on a polysiloxane column HP-5 of Agilent gas chromatography, carrying out second-order temperature programming, and keeping the initial temperature at 50 ℃ for 1 minute and then raising the temperature to 100 ℃ at a speed of 10 ℃/min; then the temperature is raised to 250 ℃ at a speed of 15 ℃/min. Carrier gas high purity N 2 Split ratio 150:1. the sample injection temperature is 250 ℃, the detector is FID, and the detector temperature is 260 ℃. The sample injection amount was 0.5. Mu.L.
The content of metal ions is measured by an R100 type ICP-AES tester.
The raw material sources are as follows: acidolysis products including 3, 6-dimethoxy-2, 7-dimethyl-4-octenedialdehyde, 3, 6-diethoxy-2, 7-dimethyl-4-octenedialdehyde, and 3, 6-diphenoxy-2, 7-dimethyl-4-octenedialdehyde, all from new and synthesized products
Example 1
Preparation of a 1# basic solid catalyst:
90g ZrOCl were added 2 To 100g of a 30% aqueous solution of magnesium nitrate, 32g of 50% aqueous ammonia was slowly added dropwise thereto with stirring. The solid was filtered and dried at 100℃for 6.0h. The solid was taken out, added to 180g of a 10% potassium nitrate solution, stirred and immersed for 10.0 hours, taken out and calcined at 400℃for 12.0 hours, and the obtained solid was designated as 1# basic solid catalyst. The catalyst obtained by ICP test had a K content of 6.2%, a Mg content of 6.0% and a Zr content of 55.3%. The surface O element content of the catalyst obtained by EDS test was 96.3%, indicating that the catalyst has a typical eggshell model. BET measurement of specific surface area of catalyst to 100m 2 ·g -1 Pore volume of 1.0 ml.g -1 The average pore diameter was 15nm.
Preparing decanal:
preheating a dichloromethane solution of acidolysis substance (3, 6-dimethoxy-2, 7-dimethyl-4-octenedialdehyde) with the mass fraction of 9.1wt% to 30 ℃, and then taking the mass space velocity of acidolysis substance as 15h -1 The reaction material enters from the upper part of the reactor, contacts with the catalyst in the catalytic section, the catalyst is filled with 0.5g, the filling volume is 10mL, the reaction is carried out at 40 ℃ under the system pressure of 0.01MPaA to generate C10 dialdehyde, the obtained reaction liquid is collected at the outlet of the lower part of the reactor, the selectivity of the liquid phase determination product is 99.2%, the total content of metal ions in the reaction liquid is 1.5ppm, the reaction is stable and runs for 30 days, the average selectivity drop rate is 0.001%/d, and the catalyst has excellent mechanical stability and chemical stability and basically no waste liquid and waste water in the reaction process.
Taking out part of reaction liquid at the outlet of the reactor, removing 50% of methylene dichloride at 30 ℃ under 0.07Mpa, cooling to 20 ℃, crystallizing to obtain C10 dialdehyde solid, wherein the purity of the crystal is 99.9% by liquid phase measurement, the content of impurity dodecenoic acid is 15.2ppm, the content of decaenol is 23.1ppm, the total content of metal ions is 7.5ppm, and the purity and the metal residue reach the standards. The obtained solid is stored for 30 days in a nitrogen atmosphere in a dark place at 30 ℃, the liquid phase continuously analyzes the content of the product in the solid, the deterioration rate of the product is only 0.001%/d, and the storage stability is good.
Example 2
Preparation of a 2# basic solid catalyst:
50g ZrOCl were added 2 To 50g of 50% aqueous magnesium nitrate solution, 10g of 50% aqueous ammonia was slowly added dropwise thereto with stirring. The solid was filtered and dried at 150℃for 10.0h. The solid was taken out, added to 50g of a 20% potassium nitrate solution, stirred and impregnated for 25.0 hours, taken out and calcined at 500℃for 15.0 hours, and the obtained solid was designated as a 2# basic solid catalyst. The catalyst obtained by ICP test had a K content of 2.1%, a Mg content of 9.0% and a Zr content of 59.1%. The surface O element content of the catalyst obtained by EDS test was 94.8%, indicating that the catalyst has a typical eggshell model. BET measurement of the specific surface area of the catalyst to 150 m2.g -1 Pore volume of 0.8 ml.g -1 The average pore diameter was 10nm.
Preparing decanal:
preheating a dichloromethane solution of acidolysis substance (3, 6-dimethoxy-2, 7-dimethyl-4-octenedialdehyde) with a mass fraction of 25.3wt% to 35 ℃, and then taking the mass space velocity of acidolysis substance as 20h -1 The reaction material enters from the upper part of the reactor, contacts with the catalyst in the catalytic section, the catalyst is filled with 0.4g, the filling volume is 8mL, the reaction is carried out at 45 ℃ under the system pressure of 0.008MPaA to generate C10 dialdehyde, the obtained reaction liquid is collected at the outlet of the lower part of the reactor, the selectivity of the liquid phase determination product is 99.5%, the total content of metal ions in the reaction liquid is 2.1ppm, the reaction is stable and runs for 30 days, the average selectivity drop rate is 0.002%/d, and the catalyst has excellent mechanical stability and chemical stability, and basically no waste liquid and waste water are generated in the reaction process.
Taking out part of reaction liquid at the outlet of the reactor, removing 50% of methylene dichloride at 35 ℃ and 0.05Mpa A, cooling to 10 ℃, crystallizing to obtain C10 dialdehyde solid, wherein the purity of the crystal is 99.9% by liquid phase measurement, the content of impurity dodecenoic acid is 21.5ppm, the content of decaenol is 20.3ppm, the total content of metal ions is 6.4ppm, and the purity and the metal residue reach the standards. The obtained solid is stored for 30 days in a nitrogen atmosphere in a dark place at 30 ℃, the liquid phase continuously analyzes the content of the product in the solid, the deterioration rate of the product is only 0.001%/d, and the storage stability is good.
Example 3
Preparation of 3# basic solid catalyst:
90g ZrOCl were added 2 To 120g of 30% aqueous magnesium nitrate solution, 60g of 50% aqueous ammonia was slowly added dropwise thereto with stirring. The solid was filtered and dried at 140℃for 12.0h. The solid was taken out and added to 200g of 15% potassium nitrate solution, stirred and immersed for 20.0 hours, then taken out and calcined at 350℃for 30.0 hours, and the obtained solid was denoted as 3# basic solid catalyst. The catalyst obtained by ICP test had a K content of 4.1%, a Mg content of 8.4% and a Zr content of 56.1%. The surface O element content of the catalyst obtained by EDS test was 97.5%, indicating that the catalyst has a typical eggshell model. BET measurement of catalyst specific surface area of 230m 2 ·g -1 Pore volume of 0.6 ml.g -1 The average pore diameter was 8nm.
Preparing decanal:
preheating a dichloromethane solution of 13.9wt% of acidolysis substance (3, 6-diethoxy-2, 7-dimethyl-4-octenedialdehyde) to 30 ℃, and taking the mass space velocity of acidolysis substance as 10h -1 The reaction material enters from the upper part of the reactor, contacts with the catalyst in the catalytic section, the catalyst is filled with 0.5g, the filling volume is 10mL, the reaction is carried out at 40 ℃ under the system pressure of 0.009MPaA to generate C10 dialdehyde, the obtained reaction liquid is collected at the outlet of the lower part of the reactor, the selectivity of the liquid phase determination product is 99.3%, the total content of metal ions in the reaction liquid is 1.8ppm, the reaction is stable and runs for 30 days, the average selectivity drop rate is 0.001%/d, the catalyst has excellent mechanical stability and chemical stability, and no waste liquid and waste water are generated basically in the reaction process.
Taking out part of reaction liquid at the outlet of the reactor, removing 50% of methylene dichloride at 33 ℃ under 0.06Mpa A, cooling to 15 ℃, crystallizing to obtain C10 dialdehyde solid, wherein the purity of the crystal is 99.9% by liquid phase measurement, the content of impurity dodecenoic acid is 12.2ppm, the content of decaenol is 25.6ppm, the total content of metal ions is 7.1ppm, and the purity and the metal residue reach the standards. The obtained solid is stored for 30 days in a nitrogen atmosphere in a dark place at 25 ℃, the liquid phase continuously analyzes the content of the product in the solid, the deterioration rate of the product is only 0.001%/d, and the storage stability is good.
Example 4
Preparation of a 4# basic solid catalyst:
100g ZrOCl 2 To 150g of a 20% aqueous solution of magnesium nitrate, 100g of 25% aqueous ammonia was slowly added dropwise thereto with stirring. The solid was filtered and dried at 170℃for 8.0h. The solid was taken out, added to 250g of a 10% potassium nitrate solution, stirred and impregnated for 15.0 hours, taken out and calcined at 280℃for 12.0 hours, and the obtained solid was designated as a 4# basic solid catalyst. The catalyst obtained by ICP test had a K content of 6.6%, a Mg content of 11.4% and a Zr content of 47.9%. The surface O element content of the catalyst obtained by EDS test was 94.9%, indicating that the catalyst has a typical eggshell model. BET measurement of specific surface area of the catalyst of 190m 2 ·g -1 Pore volume of 1.1 ml.g -1 The average pore diameter was 9nm.
Preparing decanal:
preheating a dichloromethane solution of acidolysis substance (3, 6-dimethoxy-2, 7-dimethyl-4-octenedialdehyde) with a mass fraction of 19.4wt% to 31 ℃, and then obtaining a mass space velocity of acidolysis substance of 20h - 1 enters from the upper part of the reactor, the reaction materials are contacted with the catalyst in a catalytic section, the catalyst is filled with 1.0g, the filling volume is 15mL, the reaction is carried out at 40 ℃ under the system pressure of 0.01MPaA to generate C10 dialdehyde, the obtained reaction liquid is collected at the outlet of the lower part of the reactor, the selectivity of the liquid phase determination product is 99.5%, the total content of metal ions in the reaction liquid is 1.1ppm, the reaction is stable and runs for 30 days, the average selectivity drop rate is 0.001%/d, and the catalyst has excellent mechanical stability and chemical stability and basically no waste liquid and waste water are generated in the reaction process.
Taking out part of reaction liquid at the outlet of the reactor, removing 50% of methylene dichloride at 32 ℃ under 0.07Mpa, cooling to 15 ℃, crystallizing to obtain C10 dialdehyde solid, wherein the purity of the crystal is 99.9% by liquid phase measurement, the content of impurity dodecenoic acid is 17.5ppm, the content of decaenol is 15.9ppm, the total content of metal ions is 5.6ppm, and the purity and the metal residue reach the standards. The obtained solid is stored for 30 days in a nitrogen atmosphere in a dark place at 30 ℃, the liquid phase continuously analyzes the content of the product in the solid, the deterioration rate of the product is only 0.001%/d, and the storage stability is good.
Example 5
Preparation of a 5# basic solid catalyst:
95g ZrOCl2 was added to 100g of a 30% aqueous magnesium nitrate solution, and 100g of 25% aqueous ammonia was slowly added dropwise thereto with stirring. The solid was filtered and dried at 190℃for 10.0h. The solid was taken out, added to 250g of a 10% potassium nitrate solution, stirred and impregnated for 12.0 hours, taken out and calcined at 300℃for 15.0 hours, and the obtained solid was designated as a 4# basic solid catalyst. The catalyst obtained by ICP test had a K content of 3.7%, a Mg content of 10.8% and a Zr content of 53.8%. EDS test the surface O element content of the obtained catalyst is 96.2%, which shows that the catalyst has a typical eggshell model. BET measurement of the specific surface area of the catalyst to 185m 2 ·g -1 Pore volume of 1.1 ml.g -1 The average pore diameter was 8nm.
Preparing decanal:
preheating a methylene dichloride solution of acidolysis substance (3, 6-diphenoxy-2, 7-dimethyl-4-octenedialdehyde) with a mass fraction of 15.3wt% to 28 ℃, and then taking the mass space velocity of acidolysis substance as 20h - 1 enters from the upper part of the reactor, the reaction materials are contacted with the catalyst in a catalytic section, the catalyst is filled with 1.0g, the filling volume is 15mL, the reaction is carried out at 35 ℃ under the system pressure of 0.01MPaA to generate C10 dialdehyde, the obtained reaction liquid is collected at the outlet of the lower part of the reactor, the selectivity of the liquid phase determination product is 99.4%, the total content of metal ions in the reaction liquid is 1.2ppm, the reaction is stable and runs for 30 days, the average selectivity drop rate is 0.001%/d, and the catalyst has excellent mechanical stability and chemical stability and basically no waste liquid and waste water in the reaction process.
Taking out part of reaction liquid at the outlet of the reactor, removing 50% of methylene dichloride at 30 ℃ under 0.07Mpa, cooling to 15 ℃, crystallizing to obtain C10 dialdehyde solid, wherein the purity of the crystal is 99.9% by liquid phase measurement, the content of impurity dodecenoic acid is 15.6ppm, the content of decaenol is 15.9ppm, the total content of metal ions is 5.3ppm, and the purity and the metal residue reach the standards. The obtained solid is stored for 30 days in a nitrogen atmosphere in a dark place at 30 ℃, the liquid phase continuously analyzes the content of the product in the solid, the deterioration rate of the product is only 0.001%/d, and the storage stability is good.
Comparative example 1
Preparation of 6# basic solid catalyst:
90g ZrOCl were added 2 To 100g of 30% aqueous magnesium nitrate solution was added, and 32g of 50% aqueous ammonia was slowly added dropwise thereto with stirring. The solid was filtered, dried at 100℃for 6.0 hours, and the resulting solid was designated as 6# basic solid catalyst. The catalyst obtained by ICP test had a Mg content of 12.1% and a Zr content of 58.9%. The surface O element content of the catalyst obtained by EDS test was 46.7%, indicating that the catalyst does not have a typical eggshell model. BET measurement of catalyst specific surface area of 150m 2 ·g -1 Pore volume of 0.9 ml.g -1 The average pore diameter was 20nm.
Preparing decanal:
preheating a dichloromethane solution of acidolysis substance (3, 6-dimethoxy-2, 7-dimethyl-4-octenedialdehyde) with the mass fraction of 9.1wt% to 30 ℃, and then taking the mass space velocity of acidolysis substance as 15h -1 The reaction material enters from the upper part of the reactor, contacts with the catalyst in a catalytic section, the catalyst is filled with 0.5g, the filling volume is 10mL, the reaction is carried out at 40 ℃ under the system pressure of 0.01MPaA to generate C10 dialdehyde, the obtained reaction liquid is collected at the outlet of the lower part of the reactor, the selectivity of the liquid phase measurement product is 95.2%, the total content of metal ions in the reaction liquid is 6.9ppm, the reaction is stably operated for 30 days, the average selectivity reduction rate is 0.02%/d, and the catalyst is mechanically reduced and the chemical stability is reduced.
Taking out part of reaction liquid at the outlet of the reactor, removing 50% of methylene dichloride at 30 ℃ under 0.07Mpa, cooling to 20 ℃, crystallizing to obtain C10 dialdehyde solid, wherein the purity of the crystal is 98.2% by liquid phase measurement, the content of impurity dodecenoic acid is 30.5ppm, the content of decaenol is 46.9ppm, the total content of metal ions is 26.2ppm, and the purity and the metal residue reach the standards. The obtained solid is stored for 30 days in a nitrogen atmosphere in a dark place at 30 ℃, the liquid phase is continuously analyzed for the content of the product in the solid, the deterioration rate of the product is only 0.015 percent/d, and the storage stability is obviously reduced.

Claims (21)

1. The preparation method of 2, 7-dimethyl-2, 4, 6-octatriene-1, 8-dialdehyde is characterized in that raw material acidolysis 3, 6-dimethyl/aryloxy-2, 7-dimethyl-4-octenedialdehyde is adopted to perform elimination reaction under an alkaline solid catalyst to generate deca-dialdehyde;
the acidolysis compound has a structure shown in a formula I, wherein a substituent R is methyl, ethyl, propyl or phenyl;
the alkaline solid catalyst is K 2 O/MgO-ZrO 2 By ZrO 2 As a carrier, mgO as ZrO 2 Tetragonal phase stabilizing substances, K 2 O is a modifier.
2. The process according to claim 1, wherein ZrO is present in the total mass of the basic solid catalyst 2 60-90wt% of MgO, 5-20wt% of K 2 The O content is 5-20wt%.
3. The preparation method according to claim 1, wherein the preparation method of the basic solid catalyst comprises the steps of:
(1) Dropwise adding ammonia water into an aqueous solution of zirconium salt and magnesium salt until a large amount of precipitate is generated, carrying out suction filtration on the precipitate, drying a filter cake, and grinding to obtain solid powder;
(2) And (3) immersing the solid powder obtained in the step (1) in an aqueous solution of soluble potassium salt, and roasting to obtain the required catalyst.
4. The method according to claim 3, wherein the mass ratio of the zirconium salt to ammonia in the aqueous ammonia in the step (1) is 1 to 10; the mass ratio of the zirconium salt to the magnesium salt is 1-10; the mass fraction of the ammonia water solution is 10-50%.
5. The method according to claim 4, wherein the mass ratio of the zirconium salt to ammonia in the aqueous ammonia in the step (1) is 2 to 5; the mass ratio of the zirconium salt to the magnesium salt is 3-5; the mass fraction of the ammonia water solution is 20-30%.
6. The method according to claim 3, wherein the mass fraction of potassium salt in the aqueous solution of the soluble potassium salt in the step (2) is 1 to 20%; the mass ratio of the potassium salt to the zirconium salt is 0.05-0.5; the soaking time is 5-30 hours; the roasting temperature is 200-500 ℃; the drying time is 10-30 hours.
7. The method according to claim 6, wherein the mass fraction of potassium salt in the aqueous solution of the soluble potassium salt in the step (2) is 5 to 10%; the mass ratio of the potassium salt to the zirconium salt is 0.1-0.3; the soaking time is 10-20 hours; the roasting temperature is 300-400 ℃; the drying time is 15-20 hours.
8. The process according to claim 3, wherein the catalyst has a specific surface area of 100 to 300m 2 ·g -1 The method comprises the steps of carrying out a first treatment on the surface of the Pore volume is 0.2-1.0 ml.g -1 The method comprises the steps of carrying out a first treatment on the surface of the The average pore diameter is 6-20nm.
9. The preparation method according to claim 8, wherein the specific surface area of the catalyst is 120-200m 2 ·g -1 The method comprises the steps of carrying out a first treatment on the surface of the Pore volume is 0.5-0.8 ml.g -1 The method comprises the steps of carrying out a first treatment on the surface of the The average pore diameter is 8-15nm.
10. The preparation method according to claim 1 or 2, wherein the preparation of the decadialdehyde comprises the steps of:
(a) Dissolving raw material acidolysis in an organic solvent, and pumping into a fixed bed loaded with the prepared catalyst under certain conditions;
(b) And (3) desolventizing the obtained reaction liquid, and cooling and crystallizing to obtain a product crystal.
11. The method according to claim 10, wherein in the step (a), the organic solvent is a protic solvent, an aromatic hydrocarbon, a chlorinated hydrocarbon, an ester solvent, or a mixture of these solvents.
12. The method according to claim 11, wherein in the step (a), the organic solvent is methanol, ethanol, isopropanol, hexafluoroisopropanol, benzene, toluene, xylene, methylene chloride, chloroform, dichloroethane, chlorobenzene, ethyl acetate, methyl propionate.
13. The method according to claim 11, wherein in the step (a), the organic solvent is chlorinated hydrocarbon.
14. The process according to claim 10, wherein the mass of the solvent for the elimination reaction in step (a) is 1 to 50 times the mass of the acid hydrolysis product of the raw material; the mass airspeed of the mixed reaction solution is 10h -1 ～60h -1 。
15. The process according to claim 14, wherein the mass of the solvent of the elimination reaction in step (a) is 2 to 20 times the mass of the acid hydrolysis product of the raw material; the mass airspeed of the mixed reaction solution is 15h -1 -25h -1 。
16. The process according to claim 10, wherein the reaction temperature in step (a) is-20 to 100 ℃, and the reaction pressure is preferably 0.005mpa to 0.08mpa g.
17. The method according to claim 16, wherein the reaction temperature in the step (a) is 0 to 50℃and the reaction pressure is 0.01MPaA to 0.03MPaG.
18. The method of claim 10, wherein the catalyst bulk density of step (a) is from 0.1g/mL to 2.0g/mL; the catalyst loading is 5 mL-30 mL.
19. The method of claim 18, wherein the catalyst bulk density of step (a) is from 0.5g/mL to 1.5g/mL; the catalyst loading is 10 mL-15 mL.
20. The process according to claim 10, wherein the solvent removal in step (b) is carried out at a temperature of 20 to 100 ℃, a pressure of 0.005mpa to 1.0mpa, and a temperature of-20 to 10 ℃.
21. The process according to claim 20, wherein the solvent removal in step (b) is carried out at a temperature of 30-50 ℃, a pressure of 0.01-0.1 mpa, and a temperature of-10-5 ℃.
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